Isobutanol synthesis catalyst

ABSTRACT

The invention relates to a catalyst for conversion of methanol, ethanol alone or in combination with n-propanol to isobutanol. The catalyst is a noble metal supported on at least a first phase having poorly crystalline manganese and zinc doped zirconium oxide phase containing about 71 to about 91 atomic % zirconium, about 10 to about 16 atomic % manganese and about 4 to about 8 atomic % zinc and a second phase of irregularly shaped hetaerolite-like crystals containing about 65 to about 69 atomic % manganese, about 31 to about 35 atomic % zinc and zero to about 5 atomic % zirconium embedded in the first phase. The catalyst is useful in making isobutanol.

FIELD OF THE INVENTION

The present invention relates to novel noble metal loaded MnZnZr oxidecatalysts for coupling of methanol and ethanol; or, methanol, ethanoland n-propanol to higher alcohols, and for incorporation of ethyleneinto the higher alcohols.

BACKGROUND OF THE INVENTION

Environmental and other concerns have increased the demand foroxygenated fuels components for internal combustion engines. Forinstance, methyl tert-butyl ether (MTBE), tert-amyl methyl ether (TAME)as well as ethyl tert-butyl ether (ETBE) are some potential high octaneoxygenates for gasoline engines. This increases the demand forisobutylene, for MTBE and ETBE production, and 2-methyl butylene forTAME production. These olefins can be derived by dehydrating isobutanoland 2-methyl butanol, respectively.

Catalysts, based on zirconium oxide for the conversion of synthesis gasto the foregoing alcohols, but not for the production of isobutanol frommethanol-ethanol mixtures, are disclosed in W. Keim and W. Falter,Catalysis Letters, Vol. 3, pp. 59-64, 1989 and M. Roper, W. Keim and J.Seibring, Federal Republic of Germany Patent Application No.3,524,317A1. However, it is not always practical to convert synthesisgas directly to these alcohols. Instead it is often desirable to converta mixture of methanol and ethanol in the presence of synthesis gas toisobutanol and 2-methyl butanol and other similar methyl branchedalcohols.

Other catalysts, such as gamma alumina impregnated with an inorganicbase promoters such as a basic metal salt and a Group VIII metal, aredisclosed for example in U.S. Pat. No. 3,972,952 for the vapor phaseconversion of methanol and ethanol to higher linear primary alcohols,for instance, n-butanol and n-propanol but not significant levels ofisobutanol and 2-methyl butanol.

U.S. Pat. No. 4,681,868 and U.S. Pat. No. 4,935,538 discloses thatcopper bismuth mixed metal oxide catalyst promoted with alkali couplesn-propanol to C₆ aldol products but does not disclose the conversion ofmethanol/ethanol mixtures to isobutanol and 2-methyl butanol. U.S. Pat.No. 5,095,156 discloses that methanol and higher alcohols are coupled inthe presence of magnesia, (MgO), and also discloses losses to methane,e.g., the weight % (wt %) selectivity of the water-free products inTable 7 of the patent shows a selectivity to CO and CO₂ ranging from35.8% to 67.7% and selectivity to methane ranging from 6.9% to 12.6%where methanol conversion ranged from 7.6% to 90.6% and ethanolconversion ranged from 20.4% to 99.1%. Such reactions are also discussedby W. Ueda et al. in Catalysis Letters, Volume 12, pages 97 to 104,1992, although Ueda gives no information of losses to methane.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 graphically represents a portion of the protocatalyst before fullactivation (1.5 cm=0.3 μm).

FIG. 2 graphically represents a portion of the activated catalyst aftermore than 80 hours under synthesis gas at 380° C. (1.5 cm=0.3 μm).

SUMMARY OF THE INVENTION

Disclosed herein is a novel noble metal loaded alkali metal doped MnZnZroxide family of catalysts and their method of preparation and their usein an integrated two stage process for conversion of synthesis gas toisoalcohols, particularly isobutanol. The catalysts also may be used forthe conversion of synthesis gas to mixtures of methanol and lightalcohols, particularly isobutanol. The catalysts are useful forconversion of methanol and ethanol alone or in combination withn-propanol to isoalcohols, particularly isobutanol. Also disclosedherein is the process for making and using the catalysts.

The catalysts are composed of a noble metal supported on at least afirst phase of mixed oxide crystallites containing from about 60 toabout 74 atomic % (on a metals only basis) zirconium, from about 21 to31 atomic % manganese and from about 5 to 9 atomic % zinc, and less thanabout 1 atomic % alkali, a second phase of zirconium-doped hetaeroliteparticles containing from about 65 to about 69 atomic % manganese, fromabout 31 to about 35% zinc, about 0.5 to 5 atomic % zirconium, andoptionally a trace atomic % of alkali, and a third phase containing fromabout 29 to about 55 atomic % manganese, from about 13 to 55 atomic %zinc and from about 13 to 35 atomic % zirconium. The first phase mixedoxide crystallites have a zirconium oxide-like structure having aparticle size of about 40 Å. to about 100 Å, the second phase particleshave a particle size of about 200 Å to greater than about 2000 Å, andthe third phase has a particle size of about 1000 Å to greater than 4000Å.

Also disclosed herein is a catalyst composition comprising at least afirst phase having poorly crystalline manganese and zinc doped zirconiumoxide phase containing 71 to 91 atomic % (on a metals only basis)zirconium, 10 to 16 atomic% manganese and 4 to 8 atomic % zinc and asecond phase of irregularly shaped hetaerolite-like crystals containing65 to 69 atomic % manganese, 31 to 35 atomic % zinc and 0 to 5 atomic %zirconium embedded in the first phase.

Also disclosed herein is a method of making alkali-doped noble metalloaded mixed manganese, zinc and zirconium oxide isobutanol synthesiscatalysts, comprising:

(a) coprecipitating a manganese, zinc and zirconium containing materialat essentially constant pH of from 8 to 12 from a solution containingmanganese, zinc and zirconium with alkali hydroxides to make thecorresponding oxyhydroxide;

(b) washing the precipitate to remove soluble alkali salts;

(c) calcining the precipitate from step (b) in an oxygen containing gasbetween about 360° C. and about 430° C. to form a mixed metal oxide ofthe precipitate;

(d) loading the mixed metal oxide of step (c) with a noble metal or amixture of noble metals;

(e) drying the noble metal loaded mixed metal oxide of step (d);

(f) reducing the material of step (e) in a hydrogen containing gas toproduce a highly dispersed noble metal protocatalyst.

Also disclosed herein is a method for making isobutanol, comprising:contacting a catalyst having a noble metal supported on at least a firstphase of mixed oxide crystallites containing from about 60 to about 74atomic % (on a metals only basis) zirconium, from about 21 to about 31atomic % manganese and from about 5 to about 9 atomic % zinc, less thanabout 1 atomic % alkali; a second phase of zirconium doped hetaerolitecontaining from about 65 to about 69 atomic % manganese, from about 31to about 35% zinc, from about 1 to about 5 atomic % zirconium, andoptionally a trace atomic % of alkali; and a third phase containing fromabout 29 to about 55 atomic % manganese, from about 13 to about 55atomic % zinc and from about 13 to about 35 atomic % zirconium, whereinthe first phase mixed oxide crystallites have a particle size of about40 Å to about 100 Å, wherein the second phase particles have a particlesize of about 200 Å to greater than 1000 Å, and wherein the third phasehas a particle size of about 1000 Å to greater than 4000 Å with a feedcontaining methanol and a hydrocarbonaceous material selected from thegroup consisting of ethanol, n-propanol, ethylene and propylene ormixtures thereof and synthesis gas to produce isobutanol.

Also disclosed herein is a method for incorporating a light olefin intoalcohol, comprising the steps of contacting a catalyst containing anoble metal supported on at least a first phase of mixed oxidecrystallite containing from about 60 to about 74 atomic % (on a metalsonly basis) zirconium, from about 21 to about 31 atomic % manganese andfrom about 5 to about 9 atomic % zinc, and less than about 1 atomic %alkali; a second phase of zirconium doped hetaerolite particlescontaining from about 65 to about 69 atomic % manganese, from about 31to about 35 atomic % zinc, from about 1 to about 5 atomic % zirconium,and, optionally, a trace atomic % of alkali, and a third phasecontaining from about 29 to about 55 atomic % manganese, from about 13to about 55 atomic % zinc and from about 13 to about 35 atomic %zirconium, wherein the first phase mixed oxide crystallites have aparticle size of about 40 Å to about 100 Å, wherein the second phaseparticles have a particle size of about 200 Å to greater than about 2000Å, wherein the third phase has a particle size of about 1000 Å togreater than about 4000 Å with a reactant stream containing a lightolefin selected from the group consisting of ethylene, propylene andmixtures thereof and synthesis gas and optionally methanol to produce aproduct stream containing the corresponding isoalcohols.

The present invention may suitably comprise, consist or consistessentially of the elements disclosed herein, and may be practiced inthe absence of an element or limitation not disclosed as required. Thepresent invention includes the products produced by the processesdisclosed herein.

DETAILED DESCRIPTION OF THE INVENTION

Environmental and other concerns have increased the demand foroxygenated fuels components for internal combustion engines. Forinstance methyl tert-butyl ether (MTBE), tert-amyl methyl ether (TAME)as well as ethyl tert-butyl ether (ETBE) are some potential high octaneoxygenates for gasoline engines. This increases the demand forisobutylene for MTBE and ETBE production and 2-methyl butylene for TAMEproduction. These olefins can be derived by dehydrating thecorresponding methyl branched alcohols, isobutanol and 2-methyl butanol,respectively. These alcohols in turn can be synthesized by reaction ofmethanol and ethanol in the presence of synthesis gas and a catalyst.Furthermore, if this reaction is carded out in the presence of synthesisgas and an olefin, such as ethylene, the olefin becomes incorporatedinto the product isobutanol or 2-methyl butanol and other similar methylbranched alcohols.

The present invention provides for manganese, zinc, zirconium oxidecontaining alkali and noble metal containing catalysts. Applicants havefound that the composition and microstructure of this catalystfacilitate production of isobutanol from methanol and ethanol ormethanol, ethanol and n-propanol. The noble metal is highly dispersedand selected from the group consisting of palladium and platinum, withpalladium preferred. Applicants have found that the composition andmicrostructure facilitate production of isobutanol and methyl butanols.

Although we do not wish to be bound by any specific theory, we believethat the catalyst produces higher alcohols from methanol and ethanol byconverting an equilibrium fraction of these feed alcohols to theiraldehydes or more likely a surface adsorbed equivalent thereof. Thesesurface species are needed to undergo an aldol type addition. This isthe addition of a carbon bearing the aldehydic oxygen to the carbonalpha to another aldehyde group. This results in a molecule that has acarbon bearing an alcohol group separated by one carbon atom from thecarbon atoms bearing the aldehyde group. Then, in a key step, thesemolecules dehydrate to form a transient alpha beta unsaturated aldehydebefore being rehydrogenated to the saturated alcohol. When methanol andethanol are the only feed species besides synthesis gas they firstcombine to form a surface three carbon species. This differs from a truealdol reaction as it appears that there is an attack of a C₁ species onfirst a C₂ species forming a C₃ species. This may desorb and escape thecatalyst as n-propanol or be attacked by another methanol derived C₁species forming a 4 carbon species that can eventually desorb and escapeas isobutanol. While isoalcohols, like isobutanol, might dehydrogenateto the aldehyde and undergo an aldol type addition, they cannotdehydrate since the carbon atom alpha to the carbon bearing the newlyformed hydroxyl group is quaternary, that is, it does not bear ahydrogen atom, thus the reaction reverses.

Also provided for is a method of preparation of this catalyst via theconstant temperature and pH precipitation of a complex mixed metaloxyhydroxide that after calcination, loading with the noble metal andfurther calcination, forms a first catalyst (protocatalyst). Thisprotocatalyst on exposure to synthesis gas at operating pressure andtemperatures undergoes solid state reactions which convert it into anactive and selective catalyst. Although the protocatalyst has the sameoverall global metals composition of the final catalyst, themicrostructure of protocatalyst and final catalyst are different. Theprotocatalyst, upon treatment under synthesis gas between about 360° C.and about 390° C., preferably about 380° C., results in the formation ofa catalyst having three phases.

The composition of these catalyst phases is given herein on an atomicpercentage basis excluding oxygen and noble metals. The first phase, A'in FIG. 2, which is largest in volume and available surface area, isabout 60 to about 74 atomic % (on a metals only basis) zirconium(preferably tetragonal, cubic or mixtures thereof), about 21 to about 31atomic % manganese, about 5 to about 9 atomic % zinc mixed oxide in theform of about <40 Å to about 100 Å crystallites with a ZrO₂ -likestructure that also contain a minor amount (<1%) of alkali. The noblemetal is principally associated with this phase. The noble metal may bein the form of a noble metal, a noble metal-containing alloy or mixedmetal dusters. The noble metal is highly dispersed, typically 75% to100% dispersion. The second phase, B' in FIG. 2, is comprised of largercrystallites (from about 200 Å to about 1000 Åcrystallites), with aconcomitantly lower surface area. This phase has the composition andstructure of a Zr doped hetaerolite where the Mn/Zn ratio isapproximately 2 to 1, that is about 65 to about 69 atomic % manganese,about 31 to about 35 atomic % zinc and about 0.5 to about 5 atomic %zirconium in crystallites that may also contain a small amount (0.1atomic %) of alkali metal. The third phase, C' in FIG. 2, which ispresent in an active catalyst is zirconium doped manganese-zinc phasewith a highly variable Mn-Zn ratio. These are relatively large Mn or Znrich crystallites with a highly variable composition that can range fromabout 29 to about 55 atomic % manganese, about 13 to about 55 atomic %zinc and about 13 to about 35 atomic % zirconium and range in size fromabout approximately 1000 Å to >4000 Å.

While not wishing to be bound by any particular theory, Applicantsbelieve that the overall efficiency of the catalyst in convertingmethanol with ethanol, n-propanol and light (C₂ to C₃) olefins to thecorresponding higher (iso) alcohols depends primarily on the availablesurface area of the first phase, and that one of the roles of zinc inthis phase is to maintain the noble metal highly dispersed thereon. Thepresence of the other phases are important insofar as they helpstabilize the desired active phase.

The protocatalyst is prepared by coprecipitating at an essentiallyconstant pH of between 8 and 12, preferably between 8.5 and 10 a mixedmanganese, zinc, zirconium oxyhydroxide with a base selected from thegroup of alkali hydroxides consisting of LiOH, NaOH, KOH, RbOH, CsOH andmixtures thereof. Temperatures are from about 0° C. up to about 100° C.,with suitable regard given to the freezing and boiling points of thesolutions used. Preferably, the temperature is between 50° C. and 90°C., most preferably between 60° C. and 80° C. The concentration,temperature and pH at which the co-precipitation is carried out may bevaried within the disclosed ranges to produce the protocatalyst. Anysoluble form of the transition metals manganese, zinc and zirconium,that are free of potential catalyst poisons, may be used. Manganesenitrate, zinc nitrate and zirconyl nitrate are the preferred startingmaterials. Constant effective stirring or blending of the solution isnecessary during the precipitation. The precipitated solid is thenpreferably washed with water to remove the alkali salts and othersoluble materials. If the conditions of catalyst usage require it, thesolid then may be blended with a suitable binder such as "Cab-O-Sil" ora silica or zirconia sol and extruded or formed in another suitablemanner known to those skilled in the art.

Preferably the mole ratio of Zr to the sum of the moles of Mn plus Zr isbetween about 0.41 and about 0.50, more preferably between 0.425 and0.49, while the mole ratio of Zn to the sum of the moles of Mn and Zr ispreferably between 0.29 and 0.40, more preferably between 0.30 and 0.39.

After an optional drying step, the precipitated solids are calcined,preferably in an oxygen containing gas such as air or oxygen, which isfree of typical catalyst poisons, such as sulfur compounds. The solid iscalcined at a temperature between about 360° C. and about 440° C. forone to 24 hours, preferably between 360° C. and 425° C. and mostpreferably between 370° C. and 390° C.. After calcination, the solid isthen cooled to room temperature and loaded with noble metal. Althoughthe Applicants do not wish to be bound by any particular theory, it isbelieved that the catalyst is more effective if it does not containstrong acid sites which would result in the conversion of the methanolfeed to dimethyl ether rather than to the desired higher alcohols byreaction with the corresponding reactants, e.g., ethanol, n-propanol.Hence, the noble metal compound or compounds used should not containcomponents which might engender acid sites. Materials such as ammonia oramine complexes of palladium or platinum, typically as the nitratesalts, are preferred. It is especially preferred if the amine complex ofthe noble metal is an ethanolamine (2-aminoethanol) complex. Such may bereadily obtained by dissolving the noble metal salt (e.g. palladiumnitrate) in water along with sufficient ethanolamine. The amines usedshould be sufficiently water soluble. A sufficient amount ofethanolamine is between about 9 to 36 times the molar amount of noblemetal used. After noble metal loading, the material is dried either inair or under vacuum and is ready for activation. Depending on the noblemetal precursor used, an optional air calcining step, as well as anoptional pre-reduction or pre-reduction and passivation step aswell-known by those skilled in the art, may be used.

The protocatalyst, thus obtained by coprecipitation and washing willhave at least two phases in addition to the noble metal or any addedbinder support. The first phase, Phase A in FIG. 1, is a continuousphase containing small and often poorly crystalline particles of amanganese and zinc doped zirconium oxide (preferably tetragonal or cubicor mixtures thereof) phase having about 71 to about 91 atomic % (on ametals only basis) zirconium, about 10 to about 16 atomic % manganeseand about 4 to about 8 atomic % zinc and also containing the noble metaland alkali. Embedded in this extensive phase is a second, distinctphase, Phase B in FIG. 1, of zirconium doped hetaerolite (Mn₂ ZnO₄) orhetaerolite-like crystallites (e.g., crystals that give a electron orx-ray diffraction pattern similar to Mn₂ ZnO₄) containing aboutapproximately about 65 to about 69 atomic % manganese, about 31 to about35 atomic% zinc and about 0 to about 5 atomic % zirconium. Thesehetaerolite phase crystallites range in size from approximately 500 Å toabout 2000 Å. A few large ( >0.2 micron sized) particles of ZnO,sometimes containing some Mn and alkali metal, are occasionally found inless than optimum preparations that are believed to be indicative ofinsufficiently rapid mixing and pH control during the precipitation stepor non-optimum starting metal ratios.

The overall bulk composition of the protocatalyst or catalyst expressedas atomic ratios of the metallic elements a:Mn b:Zn c:Zr has values ofbetween about 3 to about 5 for a, about 2 to about 3 for b, and about 3to about 5 for e. On the same atomic ratio scale, the value for thealkali metal coefficient is typically less than 0.1. On this material0.1 to 5 wt % palladium or about 0.2 to about 10 wt % platinum may beused with 0.2 to 2 wt % preferred and palladium preferred. Higher noblemetal concentrations unnecessarily add to the cost of the catalystwithout a significant benefit.

On reduction in hydrogen and exposure to synthesis gas at from about360° C. to 390° C., typically 380° C., the protocatalyst is transformedinto an active final catalyst phase (synthesis gas treated catalyst),the composition of which was discussed above. The reduction step istypically carded out in a manner that results in a highly dispersednoble metal phase. A typical reduction sequence would includeestablishing a flow of dry, poison-free inert gas at low pressurethrough the bed of the protocatalyst at about at least 30 SCCM/cm³ ofcatalyst volume and heating the reactor to 100° C. at 8° C./minute orless until 100° C. is achieved and holding for at least 20 seconds percm³ of catalyst volume. Thereafter, hydrogen is gradually introduced (tominimalize catalyst decomposition) into the inert gas until the hydrogenpartial pressure is between about 60 and about 80 kPa. The reactortemperature then is increased at about 8° C./minute or less until 200°C. is achieved, at which point the temperature is held for about 20sec/cm³ of catalyst. The temperature is increased at 4° C./min or lessto 260° C. and held while the partial pressure of hydrogen is increasedup to about 1 atm. or 100 kPa and the hydrogen flow rate increased toabout 300 SCCM/cm³ of catalyst. The catalyst is held under theseconditions for at least about 3 min/cm³ of catalyst. This gentlereduction sweeps reaction products from the reactor. The reactortemperature is then increased at a rate of 3° C./minute or less until upto about 380° C. to 400° C. is achieved. The catalyst is typically heldat that temperature for at least one hour before the introduction ofsynthesis gas and the increase in pressure to the operating range. It isoften advisable to decrease the temperature to about 350° C. beforesynthesis gas is introduced to avoid the occurrence of any destructiveexotherms. If the temperature is decreased before the introduction ofsynthesis gas, it may be increased at a controllable rate back to about380° C. once the synthesis gas is introduced and flowing at operatingpressure.

The synthesis gas used may have a hydrogen to carbon monoxide ratio offrom about 0.1 to 4.0, preferably 0.4 to 2.5, and most preferably fromabout 0.5 to about 1.5. The synthesis gas may contain up to 50% or morecarbon dioxide with less than 10% preferred. This synthesis gas may alsocontain light olefins, like ethylene or ethylene and propylene, duringoperation since the catalyst will incorporate a portion of these olefinsinto the higher alcohol product, but it is usually advisable tointroduce these olefins to the catalyst after the catalyst has beenoperated under synthesis gas for several hours. Of course, the synthesisgas may also contain inert gases such as nitrogen, argon and relativelyunreactive hydrocarbons like methane and ethane, etc.

While the protocatalyst can be used directly after reduction inhydrogen, it tends to be more effective if treated or held undersynthesis gas, typically from 24 to 96 hours at between 360° C. and 390°C., preferably 370° C. to 390° C., to allow the transformations (i.e.,in microstructure to produce the final catalyst) to occur (see Example23, Table 6 below).

It is important that the combination of the overall elementalcomposition and microstructure of the catalysts fall within therequirements described herein. Desirably, the result will be a catalysthaving high isobutanol selectivity and productivity at relatively lowpressures for this type chemistry (pressure up to about 1500 psig(10,350 kPa)).

The operating pressures and temperatures in the process herein are afunction of the methanol, hydrogen and carbon monoxide thermodynamics.If the temperature is too high relative to the synthesis gas pressure,methanol will be decomposed to synthesis gas. If the pressure is toohigh relative to the hydrogen partial pressure, too littledehydrogenation will occur and the rate of coupling will be slow. Theratio of methanol to ethanol, or methanol to ethanol and n-propanol canvary from 50:1 to 4: 1, with a preferred range of 15:1 and 5:1, and amore preferred range of 12:1 and 6:1. If the amount of ethanol, orethanol and propanol is insufficient, the productivity will be low. Ifthe amount of these higher alcohols is excessive, products such asn-butanol from ethanol-ethanol coupling, and 2-methyl pentanol fromn-propanol to n-propanol coupling will become significant. Depending onthe H₂ and CO partial pressures and their ratio, methanol and ethanol,or methanol, ethanol and n-propanol will be smoothly converted toisobutanol with some methyl butanols at temperatures in the range ofabout 330° C. to 355° C., and above H₂ to CO ratios of about 0.8 toabout 1.2, with combined partial pressures of about 5600 kPa to about6600 kPa.

Conversion by the catalyst is preferably greater than 505, morepreferably greater than 80%, most preferably greater than 90% of ethanolfed, and preferably above 70%, more preferably above 80%, of then-propanol fed.

Similarly, for olefin incorporation into the liquid products to beeffective, the synthesis gas hydrogen to CO ratio should be in the 0.4to 2.1 range, more preferably below 1.5. Synthesis gas with a higherhydrogen content tends to cause excessive olefin hydrogenation.

Table A below gives the composition of the various phases on a metalsmole percent basis.

                  TABLE A                                                         ______________________________________                                        Phase   Mn            Zn      Zr                                              ______________________________________                                        A       13 ± 3      6 ± 2                                                                             81 ± 10                                      B       67 ± 2     33 ± 2                                                                             2.5 ± 2.5                                    ______________________________________                                    

Phase A is composed of small, Mn doped crystallites of ZrO₂ that areresponsible for the majority of the protocatalyst surface area. Thesecrystals also contain a small mount of Zn. Phase B consists ofhetaerolite, Mn₂ ZnO₄, crystallites.

Table B describes the catalyst after treatment for more than 80 hoursunder synthesis gas at 380° C.

                  TABLE B                                                         ______________________________________                                        Phase   Mn            Zn       Zr                                             ______________________________________                                        A'      26 ± 5      7 ± 2                                                                              67 ± 7                                      B'      67 ± 2     33 ± 2                                                                              2.5 ± 2.5                                   C'       42 ± 13    34 ± 21                                                                             24 ± 11*                                   ______________________________________                                         *Dense agglomerates of the C' type are all relatively rich in Mn and Zn       but exhibit a wide range of Mn to Zn ratios.                             

Phase A' remains the high surface area phase composed of small (about 40Å to about 100 Å) Mn-doped ZrO₂ that have become enriched in Mn whiletheir Zn content hasn't significantly increased. These smallcrystallites exhibited a high concentration of stacking faults and otherdefects consistent with the presence of dopant atoms. The diffractionpatterns, obtained from these small crystallites, were broad and poorlyformed. They were most consistent with that expected for cubic ZrO₂ anddiffering only by the absence of the 102 reflection at 2.1 Å from thepattern expected of tetragonal ZrO₂. Monoclinic ZrO₂ can be ruled outsince many unique reflections expected for that structure were missing.Phase B' are hetaerolite crystallites as in the protocatalyst but areconsiderably fewer in number and smaller in size. As their diffractionpattern did not change, they gained little if any Zr during catalystactivation. The third phase, C', are dense crystallites, all relativelyrich in Mn and Zn, which exhibit a wide range of Mn to Zn ratios.

EXAMPLE 1 Preparation of Protocatalyst A with Ratio of Mn:Zn:Zr of0.38:0.26:0.30

The protocatalyst was prepared by the constant pH precipitation of a mixoxyhydroxide of Mn, Zn and Zr by a 2 Molar LiOH solution. The Mn, Zn, Zrsolution was prepared by dissolving in 500 ml of distilled water thefollowing amounts of manganese, zinc and zirconyl nitrates that wereobtained from Aldrich Chemical Company, Inc. of Milwaukee, Wis. 53233USA. 0.3 Moles, 43.06 g, Mn(NO₃)2.6 H₂ O, (F.W. 287.04), 0.2 Moles,29.70g, Zn(NO₃)₂.6H₂ O (F.W. 297.47) and about 0.4 Moles, 46.25 g,ZrO(NO₃)₂.xH₂ O (F.W. 231.23). The resulting solution was 0.9 Molar intransition metals. This solution was added over the course of 30minutes, with constant stirring, to 600 ml of water held at 70° C. ThepH of this 600 ml was initially adjusted to pH 9.0 with LiOH. Over thecourse of the addition, the addition rate of the transition metalsolution and of 2.0 Molar LiOH was controlled to maintain a pH of 9.0.Five minutes after the addition was complete, the pH was observed todrift down to about pH 7 and additional 2.0 Molar LiOH was added torestore pH 9.0. Stirring was continued overnight at 70° C., during whichtime the suspension was concentrated by water evaporation. Theprecipitate was isolated by filtration. The filtrate had a pH of 6.26.The solids were resuspended in one liter of distilled water and stirredvigorously for 30 minutes, then recovered by filtration. The pH of thefiltrate was 7.07. This washing step was repeated and the pH of thefinal filtrate was 6.20. It was dried overnight at 130° C. The driedmaterial was ground to a fine powder and calcined in air in a tubefurnace, the temperature of which was raised from room temperature to425° C. over the course of two hours, held at 425° C. for two hours, andallowed to cool to room temperature over the course of two hours. 13.79g of dry material was recovered. 10 g of this material was treated with10 ml of distilled water in which 0.0616 g of Pd(NO₃)₂ was dissolvedalong with 15 drops of ethanolamine. After thorough mixing, the slurrywas dried in a vacuum oven for six hours. The Pd-loaded and driedcatalyst was heated in air, with the temperature increased from ambientto 325° C. over the course of one hour. The temperature was held at 325°C. for three hours, then cooled over the course of one hour.

The BET surface area was 74.1 m2/g, and elemental analysis showed molefractions of the Mn, Zn, Zr and Li to be respectively 0.3841, 0.2592,0.2954 and 0.0613. The wt % Pd was 0.24%.

The calcined protocatalyst was crushed to a fine powder; a portion ofthis solid was then compressed under about 880 kg/cm² pressure using astainless steel die 2.56 cm in diameter to form wafers which were thencrushed and sieved to obtain a granular material that was retained on an80 mesh sieve after passing through a 60 mesh sieve (that is, particleswith an approximate size of about 180 μm to about 250 μm in diameter).3.0 cm³ of this material, 3.9850 g, was mixed with 6 cm³, 7.1860 g, of40-60 mesh (that is, about 250 μm to 425 μm in diameter), crushed, highpurity, acid washed and calcined quartz as a diluent. The resultingmixture was charged to a copper-jacketed, copper-lined stainless steelreactor tube (net I.D. 0.41 inch, 1.0414 cm) equipped with acopper-jacketed 0.125 inch (0.3040 era) outside diameter thermowell.This reactor was attached to a flow system by means of "VCR" fittings.The catalyst bed was flushed with high purity argon, and then 240 SCCMhigh purity hydrogen and 180 SCCM high purity argon under an exitpressure of 300 kPa were passed through the catalyst bed as it washeated to 240° C. over the course of 120 minutes. After a one minutehold at 240° C., the argon was turned off and the hydrogen flow rate wasincreased to 1200 SCCM. The catalyst bed was then heated to 260° C. at8° C./min and held there for five minutes, then heated at 2° C./min. to400° C. and held there for one hour, after which time the reactor wascooled to 350° C. at 8° C./minute and held at 350° C. while gascomposition was changed to synthesis gas and the system pressurized toabout 6540 kPa at the outlet of the catalyst bed. Once synthesis gasflow was established, the catalyst bed could then be heated back to 380°C. at 3° C./min without overheating. The synthesis gas mixture usedcontained 44.0% carbon monoxide, 39.4% hydrogen, 10.0% argon and 6.6%carbon dioxide. It was held at 380° C. for 92 hours before thetemperature was decreased to 360° C. and at 360° C. for an additional 20hours before the temperature was decreased to 340° C. After 16 hours at380° C., a methanol ethanol water mixture was introduced and vaporizedbefore the catalyst such that the gas composition entering the catalystbed was approximately 44% CO, 39.4% H2, 6.6% CO₂ and 10.0% Ar synthesisgas, into which was vaporized at a rate of 0.8 liquid hourly spacevelocity a mixture of 90.00 wt % methanol, 9.56 wt % ethanol and 0.44%water. The overall gas hourly space velocity was then about 8500 V/V/hr.

Analytical transmission electron microscopy was used to characterize thecomposition and structure of phases in protocatalyst A, and in the sameafter activation, and used as an alcohol coupling catalyst. Thecomposition (Zr, Mn, Zn) was determined for regions as small as 4 nm (40Å) using a 200 kV accelerating voltage Philips CM20 field-emissiontransmission electron microscope equipped with energy-dispersive x-ray(EDX) analysis. Catalyst particles were embedded in an epoxy and thenmicrotomed into about 500 Å-thick slices in order to determine themorphologies of the large scale structures (about ≦1 μm) whilesimultaneously making it possible to observe individual small Zr-richand Mn-rich phases. Quantitative EDX analyses were carried out usingmacroscopic (about 5 μm) sampling regions of the starting catalyst asstandards for determining k-factors that were subsequently used foranalysis of smaller regions in starting and treated catalysts. The smallprobe available in this field-emission instrument (about 2 nm diameter)made it possible to isolate the EDX signal from individual particles assmall as 4 nm with efforts taken to minimize contributions fromneighboring particles. Noble metals were located in Zr-rich regionsusing a Philips EM420ST TEM operated at 100 kV using large samplingregions in Zr-rich or Zr-depleted regions and energy-dispersive x-rayanalysis.

Protocatalyst A was found by transmission electron microscopy to have atleast two phases in addition to palladium metal. The first phase is acontinuous phase containing small (about 40 Å to 50 Å) and often poorlycrystalline (as evidenced by the broad electron diffraction lines)particles of a manganese and zinc doped zirconium oxide phase containingabout 71 to about 91 atomic % (on a metals only basis) zirconium, about10 to about 16 atomic % manganese and 4 to about 8 atomic % zinc on anmetals only basis. On the basis of electron diffraction patterns, thezirconium dioxide is believed to have a cubic structure. Embedded inthis extensive zirconium rich phase is a second, distinct phase ofirregular hetaerolite (Mn₂ ZnO₄) or hetaerolite-like crystallites (e.g.,crystals that give an electron or x-ray diffraction pattern similar toMn₂ ZnO₄) containing approximately about 65 to about 69 atomic %manganese, about 32 to about 35 atomic % zinc and about 0 to about 5atomic % zirconium. These range in size from about approximately 500 fitto about approximately 2000 Å.

After activation and use the catalyst was found to have three phases inaddition to palladium. The continuous, higher surface area, Zr richphase had gained Mn and some Zn, while the hetaerolite-like crystalliteshad decreased considerably in size and number and a third phase ofvariable composition with variable Mn/Zn ratio had appeared. The firstphase, which was largest in volume and available surface area, containedon a metals only basis about 60 to about 74 atomic % (on a metals onlybasis) zirconium, about 21 to about 31 atomic % manganese, about 5 toabout 9 atomic % zinc in the form of about 40 Å to about 100 Åcrystallites. Compared to the protocatalyst, these are enriched in Mn,while their Zn content was not significantly increased. These smallcrystallites exhibited a high concentration of stacking faults and otherdefects consistent with the presence of dopant atoms. The diffractionpatterns obtained from these small crystallites were broad and poorlyformed. Their diffraction patterns were most consistent with thatexpected for cubic ZrO₂ and differing only by the absence of the 102reflection at 2.1 Å from the pattern expected of tetragonal ZrO₂.Monoclinic ZrO₂ can be ruled out since many unique reflections expectedfor that structure were missing. Embedded in this extensive zirconiumrich phase are irregular hetaerolite (Mn₂ ZnO₄) or hetaerolite-likecrystallites (e.g., crystals that give an electron or x-ray diffractionpattern similar to Mn₂ ZnO₄). These were smaller in size (200Å toapproximately 1000 Å across) and fewer in number than in theprotocatalyst and contained approximately the same concentration ofmanganese, zinc and zirconium as in the protocatalyst, that is, about 65to about 69 atomic % manganese, about 31 to about 35 atomic % zinc andabout 0 to about 5 atomic % zirconium, and gave the same diffractionpattern as in the protocatalyst. A significant increase in Zr would beexpected to alter this pattern as the Zr atom is significantly larger indiameter than either Mn or Zn. Also embedded in the continuous Zr richphase of the active catalyst was a new phase consisting of densecrystallites all relatively rich in Mn and Zn but which exhibit a widerange of Mn to Zn ratios. This latter phase varies in size as well ascomposition ranging from about approximately 1000 Å to >4000 Å and fromabout 29 to about 55 atomic % manganese, about 13 to about 55 atomic %zinc and about 13 to about 35 atomic zirconium. This phase is largeenough to be clearly visible with a scanning electron microscope when abackscattered electron detector was used to obtain average atomic numberimages of the sample.

EXAMPLE 2 Preparation of Protocatalyst B with a Mn:Zn:Zr Ratio of 0.39:0.27:0.34

This example illustrates the preparation and activation of Catalyst B, acatalyst within the preferred scope of this invention. 0.3 moles, 43.06g, Mn(NO₃)₂.6H₂ O, (F.W. 287.04), 0.2 moles, 29.70 g, Zn(NO₃)₂.6H20(F.W. 297.47) and about 0.4 moles, 46.25 g, ZrO(NO₃)₂.xH₂ O (F.W. 231.23) were dissolved in 500 mi distilled water to make solution TM.Similarly, 42 g of LiOH.H₂ O were dissolved in one liter of distilledwater to make a 1 Molar solution of LiOH designated solution B. At arelative rate of 2.7 for solution TM and 1 for solution B, these twosolutions were added with rapid stirring to 600 ml of distilled water at70° C. such that the pH of the resultant slurry was maintained at 9.0±0.2. The resultant light pinkish precipitate was allowed to cool toroom temperature (ca 22° C.) and settle overnight. On filtering off thesupernatant, which had a pH of 8.59, a light brown solid was recovered.This was washed with three one-liter portions of distilled water. The pHof the filtrate from each washing was respectively 8.32, 8.15 and 7.56.

After drying in a glass container at 130° C. in air for an extendedperiod of time, 36 g of the dry material were calcined to 380° C. inair. 15 g of the calcined material was then palladium loaded as follows:376 mg of Pd(NO₃)₂.xH₂ O were dissolved in 20 ml of distilled wateralong with 30 drops of ethanolamine. The solid and the solution werecombined and mixed thoroughly and then dried in a vacuum oven for twohours prior to calcining. The dried solid was heated in air over thecourse of one hour to 380° C., held at 380° C. for one hour, and thencooled to room temperature over the course of one hour.

The resulting material had a surface area of 75.1 M² /g and the atomicfractions of Mn, Zn, Zr and Li were respectively 0.3857, 0.2706, 0.3428and 0.0010.

The material had a Pd concentration of 1.21 wt %. A portion of thissolid was then compressed using a stainless steel die to form a waferwhich was then crushed and sieved to obtain a granular material that wasretained on an 80 mesh sieve after passing through a 60 mesh sieve, thatis the granules had a size range of about 180 μm to about 250 μm. 3.0cm³ of this material, 3.3952 g, were mixed with 6 cm³, 8.0937 g, of40-50 mesh crushed high purity, acid washed and calcined quartz as adiluent, that is, the irregular quartz chunks were from about 300 μm to425 μm in diameter. The resulting mixture of catalyst and quartzgranules was charged to a copper-jacketed, copper-lined stainless steelreactor tube (net I.D. 0.41 inch, 1.0414 era), equipped with acopper-jacketed 0.125 inch (0.3040 cm) outside diameter thermowell. Thisreactor was attached to a flow system by means of "VCR" fittings. Thecatalyst bed was flushed with high purity argon, and then 240 SCCM highpurity hydrogen and 180 SCCM high purity argon under an exit pressure of300 kPa were passed through the catalyst bed as it was heated to 200° C.over the course of 15 minutes. After a one minute hold at 200° C., thecatalyst bed was heated at 4° C./min to 260° C. During a one minute holdat 260° C., the argon was turned off and the hydrogen flow rate wasincreased to 1200 SCCM. Under this condition, the reactor bedtemperature was increased at 3° C./min to 377° C. without overheating.After 60 minutes at 377° C., the temperature was decreased to 350° C.and the gas composition changed to a carbon monoxide, hydrogen, argon,carbon dioxide, blend flowing at about 400 SCCM through the catalyst bedand the reactor pressure was slowly increased to 6500 kPa. The synthesisgas mixture used contained 44.0% carbon monoxide, 39.4% hydrogen, 10.0%argon and 6.6% carbon dioxide. Once this gas mixture was flowing throughthe system and the reactor pressure was stabilized at about 6550 kPa,the reactor temperature was increased to 377° C. Under these conditionsthe temperature at the exit of the catalyst bed was about 380° C. Theresultant liquid produced from the synthesis gas was about 29.4% water,67.3% identified organic compounds: methanol, methyl formate, ethanol,n-propanol, isobutanol, n-butanol, 3-methyl 2-butanol, 3-pentanol,3-methyl- 1 -butanol, 2-methyl- 1 -butanol, 4-methylpentanol,n-pentanol, 2,2-dimethyl 3-pentanone, 2-methyl-l-pentanol, and 2,4dimethyl-3-pentanol and about 3.3% trace, unidentified organiccompounds. The identified organics were 73.6% methanol, 19.6%isobutanol, 1.8% n-propanol, 1.3% methyl butanols and 3.7% othermaterials on a carbon basis.

EXAMPLE 3

This example illustrates the performance of Catalyst B with a methanol,ethanol, water feed.

After the gas composition of Example 9 (at 380° C.) was changed to 47.1%carbon monoxide, 42.2% hydrogen and 10.7% argon, a 90 wt % methanol,9.56% ethanol and 0.44% water vapor was added to the gas mixture and fedto the catalyst. Under these conditions, 99.7% of the ethanol wasconverted to C₃ +products through reaction with the methanol. Somemethanol was also decomposed into hydrogen and carbon monoxide. In thiscase, the liquid produced was 11.4% water, 87.4% identifiable organiccompounds: methanol, methyl formate, ethanol, n-propanol, isobutanol,n-butanol, 3-methyl-2-butanol, 3-pentanol, 3-methyl-l-butanol,2-methyl-l-butanol, 4-methyl-pentanol, n-pentanol,2,2-dimethyl-3-pentanone, 2-methyl-1 -pentanol, and2,4-dimethyl-3-pentanol and 1.2% trace materials. On a carbon basis, theproduced liquid was 45.9% isobutanol, 35% methanol, 4.4% methylbutanols, 4.4% n-propanol, 1.7% 2-methyl-l-pentanol with about 0.13%ethanol and 7.8% miscellaneous organic compounds.

EXAMPLE 4

This example illustrates that Catalyst B, a catalyst within thepreferred scope of this invention, is effective in converting amethanol, ethanol, water and n-propanol feed in the essential absence ofundesirable hydrocarbons.

The reactor temperature in Example 3 was decreased from about 380° C. toabout 340° C. and the liquid feed composition was changed to resemblethe liquid produced without the methanol-ethanol vapor feed. Under theseconditions, little, if any, methanol was decomposed into gas, and lessthan 0.1% of the carbon passing through the reactor was converted tohydrocarbon gas. The liquid composition was changed to about 87.2 wt %methanol, 7% ethanol and 5.8% n-propanol. Under these conditions, theethanol conversion was 90.2% and the n-propanol conversion was 74.9%.The resultant liquid product contained 86.3% identified organicproducts: methanol, methyl formate, ethanol, n-propanol, isobutanol,n-butanol, 3-methyl-2-butanol, 3-pentanol, 3-methyl-l-butanol,2-methyl-l-butanol, 4-methyl-pentanol, n-pentanol,2,2-dimethyl-3-pentanone, 2-methyl-l-pentanol, and2,4-dimethyl-3-pentanol, 8.9% unidentified organic products and 4.8%water. On a carbon basis, the liquid product contained about 67.7%methanol, 24.4% isobutanol, 2.6% methyl butanols along with 3.5%n-propanol and 1.4% ethanol.

Increasing the temperature of the reactor in Example 4 from 340° C. to350° C. increased the ethanol conversion to 97.8% and the n-propanolconversion to 88% after over 190 hours on-line. The liquid producedcontained on a carbon basis 62.1% methanol, 30.8% isobutanol, 2.1%methyl butanols, along with 0.4% ethanol and 1.9% n-propanol.

EXAMPLE 5

This example illustrates the incorporation of a light olefin, ethylene,into the alcohol product when ethylene is co-fed to the catalyst, alongwith methanol, ethanol, n-propanol and synthesis gas.

Under the final conditions of Example 4 (350° C. and about 6550 kPa),the feed gas was changed to 44.0% carbon monoxide, 39.4% hydrogen, 10.0%argon and 6.6% polymer grade ethylene. Under these conditions about 25%of the ethylene fed was converted with 80% selectivity to liquids, 19%to ethane and 1% to higher hydrocarbons including n-butane and butenes.The liquid produced on a carbon basis was: 59.3% methanol, 32.4%isobutanol, 2.3% methyl butanols, 2.2% n-propanol, 1%2-methyl-l-pentanol and 0.4% ethanol along with miscellaneous organiccompounds. With an ethylene co-feed, the ethanol conversion was about97.4% and the n-propanol conversion was about 86.2%. These values werecomparable to, or slightly lower than, those without ethylene feed. Withethylene co-fed, the concentration of unidentified organic compounds inthe liquid increased from 1.1% to 3.2%. Significantly, ethylene co-feedalso increased the productivity of isobutanol by 7.8% and that of methylbutanols by 11%.

EXAMPLE 6

This example illustrates the conversion and disposition of carbondioxide free synthesis gas and a methanol, ethanol, n-propanol liquidfeed over a catalyst within the scope of this invention.

A second 3.0 cm³ (3.1215 g) sample of 60 to 80 mesh (180 μm to 250 μ)granules of Protocatalyst B were blended with 6.0 cm³ (6.8880 g) of acidwashed and calcined high purity fused quartz crushed and sieved to 40 to60 mesh (250 μm to 425 μm). This mixture was charged into acopper-jacketed, copper-lined stainless steel reactor tube (net I.D.0.41 inch, 1.0414 cm) equipped with a copper-jacketed 0.125 inch (0.3040cm) outside diameter thermowell. This reactor was attached to a flowsystem by means of "VCR" fittings. The catalyst bed was flushed withhigh purity argon, and then 240 SCCM high purity hydrogen and 180 SCCMhigh purity argon under an exit pressure of 300 kPa were passed throughthe catalyst bed as it was heated to 200° C. over the course of 30minutes. Then, after a one minute hold at 200° C., it was heated to 260°C. over the course of 30 minutes. After one minute at 260° C., the argonwas turned off and the hydrogen flow rate was increased to 1200 SCCM.The catalyst bed was then heated to 377° C. over the course of about 50minutes, then held there for one hour, after which time the reactor wascooled to 350° C. at 2° C./min and held at 350° C. while gas compositionwas changed to synthesis gas and the system pressurized to about 6540kPa at the outlet of the catalyst bed. Once synthesis gas flow wasestablished, the catalyst bed could then be heated back to 380° C. inthe catalyst bed at 3° C./min without overheating. Once the catalystreached 380° C. under synthesis gas flowing at 400 SCCM, it was"on-line" and the run time clock was started. The synthesis gas mixtureused contained 47.5% carbon monoxide, 42.5% hydrogen and 10.0% argon.After 41 hours on-line, a mixture of 87.41% methanol, 6.42% ethanol,5.85% n-propanol and 0.32 wt % water was vaporized into the synthesisgas above the catalyst bed at the rate of 2.4 cm³ of liquid at 0° C. perhour. The catalyst bed was held at 380° C. for 64 hours before thetemperature was decreased to 350° C.

After 70 hours on-line at a catalyst bed temperature of 350° C. and afeed synthesis gas composition of 47.10 mole % CO, 42.17 mole % H₂ and10.73 mole % Ar as an internal standard, the carbon monoxide conversionwas about 1.8%. This was determined using a gas chromatograph thatalternately sampled feed and product gas streams. All the gas feeds tothe experimental reactor are controlled with electronic mass flowcontrollers working with a constant feed and back pressure. Thus theflow of the individual gases and of the mixed gas feed to the reactor iseffectively constant. Thus, the Molar ratio of carbon monoxide to argonin the feed and product should be constant in the absence of reaction.If a carbon monoxide-consuming reaction occurs over the catalyst, thenthe ratio of feed carbon monoxide, CO_(f), to feed argon Ar_(f) mustequal the ratio of product carbon monoxide, CO_(p), plus carbon monoxideconsumed, CO_(c), to product argon, Ar_(p), that is:

    CO.sub.f /Ar.sub.f =(CO.sub.p +CO.sub.c /Ar.sub.p or CO.sub.c =(Ar.sub.p CO.sub.f -Ar.sub.f CO.sub.p)/Ar.sub.f

A gas chromatograph was used to alternately sample feed and product gas.The carbon selectivity of this converted gas was found to be about 39.2%to carbon dioxide, 60.8% to hydrocarbon gases and effectively none toliquids using the carbon bookkeeping convention that carbon fromconvened carbon monoxide is first assigned to the observed net carbondioxide (excess of CO₂ in the exit gas over that fed), then to theobserved hydrocarbon gases. The balance of the consumed carbon is thenassigned to the liquid product, that is:

    Moles of CO converted-(moles CO.sub.2 produced+moles carbon as hydrocarbon gases)=moles CO convened to liquid.

The carbon distribution of the hydrocarbon gases was: 28.8 C % ethylene,24.7 C % propylene, 18.8 C % isobutylene, 12.4 C % methane, 11.8 C %ethane, 2.3 C % propane and 1.2 C % isobutane. This composition suggeststhat most of these gases, with the exception of the methane, arose fromthe dehydration of the alcohols fed (or produced), forming olefins, withthe subsequent hydrogenation of some of these olefins to form paraffins.These data also show that the losses to methane are on the order of 0.2%of the carbon passing through the reactor. The liquid product producedat the same time as above the gaseous products (that is, the liquidcollected between 68.5 and 71 hours on-line) contained about 7wt % waterand 93 wt % organic products, of which 99% were identifiable. Thebreakdown of these organic products on a carbon percent basis is asfollows: 62.41 C % methanol, 30.23 C % isobutanol, 2.08 C % n-propanol,1.96 C % methyl butanols, 0.90 C % ethanol, 0.88 C % 2-methyl pentanol,0.09 C % n-butanol and about 1.45 C % miscellaneous organic products.This represents about 95.1% ethanol conversion, 88.7% n-propanolconversion. On a methanol, water free basis, the C2+liquid products wereabout 80 wt % isobutanol, 6 wt % n-propanol, 5 wt % methyl butanols, 3.0wt % ethanol and about 6 wt % other products.

EXAMPLE 7

This example demonstrates the performance of a catalyst within the scopeof this invention for the incorporation of a light olefin, ethylene,into the liquid product produced from carbon monoxide and hydrogen.

After 77 hours on-line, the gas composition over the catalyst in Example6 was changed to 43.7 mole % CO, 39.1 mole % H₂, 9.9 mole % Ar and 7.3mole % polymerization grade ethylene. After 89 hours, the liquid feedwas turned off and the behavior of the thoroughly activated, lined-outcatalyst under the ethylene containing synthesis gas was monitored bygas chromatography using argon as an internal gas standard as above.Using the carbon bookkeeping convention that ethylene could be convertedto only ethane or liquid products and that CO could be converted to CO₂,liquids or hydrocarbon gases except ethane and ethylene, the followingresults were obtained: Under these conditions 16.2% of the ethylene fedwas converted to products. The carbon selectivity to ethane was 72.3carbon % and the selectivity to liquid products 27.7 carbon %. At thesame time, the CO conversion averaged 4.3 mole %. Of this, 92.7% on acarbon basis was converted to liquid products, 2.7 C % to carbon dioxideand the balance, 7.3 C % to hydrocarbon gases (except for ethane andethylene). The breakdown of the hydrocarbon gases on a carbon % basiswas as follows: 31.04 C % n-butane, 27.09 C % methane, 10.84 C %propylene, 9.74 C % isobutylene, 6.79 C % isopentene, 6.25 C % propane,3.79 C % isopentane, 2.53 C % n-butenes, 1.19 C % n-pentane, and 0.11 C% isobutane, along with about 0.63 C % hexenes and hexanes. The liquidproduct was about 5% water and 95% organic products by weight. Theorganic products on a carbon % basis were derived 72.7% from the CO thatwas converted and 27.3% from the ethylene that was converted. It isbelieved that the carbon derived from the incorporated ethylene is inthe C₂ + products, especially in the C₄ + products. The composition ofthe liquid products on a carbon basis was: 90.02 C % methanol, 5.81 C %isobutanol, 0.37 C % methyl-butanols, 0.35 C % n-propanol, 0.18 C % 2methyl-1-pentanol, 0.08 C % ethanol and 0.07 C % n-butanol, with thebalance of the carbon in other miscellaneous oxygen-containing organicproducts.

EXAMPLE 8

This example further illustrates the incorporation of an olefin,ethlyene, into the liquid product derived from synthesis gas and amethanol, ethanol, n-propanol liquid feed.

After 165 hours on-line, the 87.41% methanol, 6.42% ethanol, 5.85%n-propanol and 0.32 wt % water liquid feed was once again vaporized intothe synthesis gas (43.7 mole % CO, 39.1 mole % H₂, 9.9 mole % Ar and 7.3mole % polymerization grade ethylene) above the catalyst bed at the rateof 2.4 cm³ of liquid (at 0° C.) per hour.

Under these conditions, 8.1% of the ethylene was converted with a carbonselectivity of 26.2% to ethane and 73.8% to "liquid products" with thesame convention for carbon book keeping as above. Similarly, 2.5% of thecarbon monoxide fed was consumed, being converted with a carbonselectivity of 72.5% to liquids, 21.4% to carbon dioxide and 6.1% tohydrocarbon gases except for ethane and ethylene. The breakdown of thehydrocarbon gases produced was on a carbon % basis as follows: methane24.58 C %, propylene 20.79C %, n-butane 19.63 C %, isobutylene 18.04C %,propane 6.60C %, isopentene 4.92 C %, isopentane 2.24 C %, n-butenes2.07 C %, n-pentane 0.82 C % and isobutane 0.31 C %.

The liquid product was about 4% water and about 96% organic products.66.2% of the carbon in these products was derived from the feedmethanol, 13.6% from the feed ethanol and propanel, 10.6% from the feedethylene and 9.6% from the feed carbon monoxide. These organic productscontained on a carbon % basis: 63.24% methanol, 27.21% isobutanol, 3.96%n-propanol, 1.96% methyl butanols, 1.00% ethanol, 0.83% 2-methylpentanol and 0.16% n-butanol with about 1.64% miscellaneous products.

EXAMPLE 9 Preparation of Protocatalyst C with a Mn:Zn:Zr Ratio of 0.42:0.29:0.29

In 500 ml of distilled water 21.53 g Mn(NO₃)₂.6 H20, 14.85 gZn(NO₃)₂.6H20(F.W. 297.47) and 23.12gZrO(NO₃)₂.xH₂ O were dissolved.This solution was added over the course of 30 minutes, with constantstirring, to 600 mi of water held at 70° C. The pH of this 600 ml wasinitially adjusted to pH 9.0 with LiOH. Over the course of the addition,the addition rate of the transition metal solution and of a 21.0 g/lsolution of LiOH was controlled to maintain a pH of 9.0. On addition ofthe transition metal solution and lithium hydroxide, the precipitateslurry was brown from the outset. Stirring was continued for five hoursat 70° C. The suspension was allowed to settle overnight at roomtemperature without stirring. The precipitate was isolated byfiltration, then washed three times by resuspension and stirring in aliter of distilled water for an hour at room temperature, followed byfiltering to recover the solids for further resuspension. The washedsolids were dried overnight at 130° C. The dried material was ground toa fine powder and calcined in air in a tube furnace, the temperature ofwhich was raised from room temperature to 425° C. over the course of twohours, held at 425° C. for two hours and allowed to cool to roomtemperature over the course of two hours. 16.35 g of dry material wasrecovered. 15.0 g of this material were treated with 15 ml of distilledwater in which 0.0939 g of Pd(NO₃)₂.xH₂ O (assay 39.95 wt % Pd) wasdissolved along with 15-20 drops of ethanolamine. After thorough mixing,the slurry was dried in a vacuum oven at 80° C. overnight. ThePal-loaded and dried catalyst was heated in air with the temperatureincreased from ambient to 325° C. over the course of one hour. Thetemperature was held at 325° C. for three hours, then cooled over thecourse of one hour.

The BET surface area was 72.1 m2/g, and elemental analysis showed molefractions of the Mn, Zn, Zr and Li to be respectively 0.4202, 0.2914,0.2884 and 0.0613. The wt % Pd was 0.24%.

EXAMPLE 10 Preparation of Protocatalyst D with a Mn:Zn:Zr Ratio of 0.40:0.28:0.32

In 500 ml of distilled water 21.53 g, Mn(NO₃)₂.6 H₂ O, 14.85 g,Zn(NO₃)₂.6 H₂ O and 23.12 g, ZrO(NO₃)₂.xH₂ O were dissolved. Thissolution was added over the course of 30 minutes, with constantstirring, to 600 ml of water held at 70° C. The pH of this 600 ml wasinitially adjusted to pH 9.0 with LiOH. Over the course of the addition,the addition rate of the transition metal solution and of a 21.0 g/ 500ml solution of LiOH was controlled to maintain a pH of 9.0. On additionof the transition metal solution and lithium hydroxide, the precipitateslurry was lighter in color than similar precipitations conducted at 70°C. Stirring was continued for five hours at 25° C. The suspension wasallowed to settle for about 60 hours at room temperature withoutstirring. The precipitate was isolated by filtration, then washed threetimes by resuspension and stirring in a liter of distilled water for anhour at room temperature, followed by filtering to recover the solidsfor further resuspension. The washed solids were dried overnight at 130°C. The dried material was ground to a fine powder and calcined in air ina tube furnace, the temperature of which was raised from roomtemperature to 425° C. over the course of two hours, held at 425° C. fortwo hours, and allowed to cool to room temperature over the course oftwo hours. 15.25 g of dry material were recovered. 15.0 g of thismaterial were treated with 15 ml of distilled water in which 0.0940 g ofPd(NO₃)₂.xH₂ O (assay 39.95 wt % Pd) was dissolved along with 15-20drops of ethanolamine. After thorough mixing, the slurry was dried in avacuum oven at 130° C. for two hours. The Pd-loaded and dried catalystwas heated in air with the temperature increased from ambient to 325° C.over the course of one hour. The temperature was held at 325° C. forthree hours; then cooled over the course of one hour.

The BET surface area was 78.8 m2/g, and elemental analysis showed molefractions of the Mn, Zn and Zr to be respectively 0.4023, 0.2823, and0.3 154. The wt % Pd was 0.25%.

EXAMPLE 11 (Comparative) Preparation of Catalyst E with a Mn:Zn:Zr Ratioof 0.54: 0.29:0.17

In 500ml of distilled water 0.10moles, 28.70g, Mn(NO₃)₂.6H₂ O, 0.05moles, 11.56 g, ZrO(NO₃)₂.xH₂ O and 0.05 moles, 14.87 g, Zn(NO₃)₂.6H₂ Owere dissolved, making a solution that was 0.4 Molar in transitionmetals. A LiOH solution was prepared by dissolving 21.0 g of LiOH in 500ml distilled water. The transition metal solution was added over thecourse of 30 minutes, with constant stirring, to 600 ml of water held at70° C. The pH of this 600 ml was initially adjusted to pH 9.0 with LiOH.Over the course of the addition, the addition rate of the transitionmetal solution and of 1.0 Molar LiOH was controlled to maintain a pH of9.0±1.0. Five minutes after the transition metal solution addition wascomplete, the pH dropped to about 7.0 and more LiOH solution was addedto bring it back up to 9.0. The precipitate was a light tanish brown incolor. Stirring was continued overnight at 70° C., during which time thesuspension was concentrated by water evaporation. The precipitate wasisolated by filtration. The filtrate had a pH of 6.26. The solids wereresuspended in one liter of distilled water and stirred vigorously for30 minutes, then recovered by filtration. The pH of the filtrate was7.07. This washing step was repeated and the pH of the final filtratewas 6.20. The solid appeared to get darker in color and more difficultto filter as the washing proceeded. The solid was dried overnight at130° C. and 13.91 g era black material were recovered. The driedmaterial was ground to a fine powder and calcined in air in a tubefurnace, the temperature of which was raised from room temperature to425° C. over the course of two hours, held at 425° C. for two hours andallowed to cool to room temperature over the course of two hours. 13.79g of dry material were recovered. 10 g of this material were treatedwith 10 ml of distilled water in which 0.0616 g of Pd(NO₃)₂.xH₂ O(Johnson Matthey) were dissolved along with 15 drops of ethanolamine.After thorough mixing, the slurry was dried in a vacuum oven for 6hours. The Pd-loaded and dried catalyst was heated in air with thetemperature increased from ambient to 325° C. over the course of onehour. The temperature was held at 325° C. for three hours, then cooledover the course of one hour.

The BET surface area was 59 m² /g, and elemental analysis showed molefractions of the Mn, Zn, Zr and Li to be respectively 0.5390, 0.2892,0.1674 and 0.0044. The wt % Pd was 0.24%.

EXAMPLE 12 (Comparative) Preparation of Catalyst F with a Mn:Zn:Zr Ratioof 0.27: 0.22:0.51

In 500 ml of distilled water 28.42 g MnCNO₃)₂.6H₂ O, 23.05 gZn(NO₃)₂.6H₂ O and 74.79 g ZrO(NO₃)₂.xH₂ O were dissolved. The LiOHsolution used to precipitate this was prepared by dissolving 42.0 gofLiOH.H₂ O (F.W. 41.96) in a liter of distilled water. The transitionmetal nitrate solution, added over the course of 30 minutes, withconstant stirring, to 600 ml of water held at 70° C. The pH of this 600ml was initially adjusted to pH 9.0 with LiOH. Over the course of theaddition, the addition rate of the transition metal solution and of 1.0Molar LiOH was controlled to maintain a pH of 9.0. Stirring wascontinued for five hours at 70° C. The suspension was then allowed tosettle and cool overnight. The tan-brown gelatinous precipitate wasisolated by filtration. The solid was washed three times by resuspensionin one liter of distilled water and 30 minutes of vigorous stirringprior to filtration. The recovered solids were dried overnight at 130°C., leading to the recovery of 45.5 g of material. The dried materialwas ground to a fine powder and 20.0 g was calcined in air in a tubefurnace, the temperature of which was raised from room temperature to425° C. over the course of two hours, held at 425° C. for two hours andallowed to cool to room temperature over the course of two hours. 13.46g of cooled, calcined material were recovered. This material was treatedwith 10 ml of distilled water in which 0.0939 g of Pd(NO₃)₂ wasdissolved along with 15 drops of ethanolamine. After thorough mixing,the slurry was dried in a vacuum oven at 110° C. for six hours. Thedried material was then calcined in air as follows: the temperature wasincreased from room temperature to 325° C. over the course of an hour,then held at 325° C. for three hours before cooling to room temperatureover the course of two hours.

The BET surface area was 112.2 m² /g, and elemental analysis showed molefractions of the Mn, Zn, Zr and Li to be respectively 0.2663, 0.2184,0.5116 and 0.0037. The wt % Pd was 0.22%.

EXAMPLE 13 (Comparative) Preparation of Catalyst G with a Mn:Zn:Zr Ratioof 0.46: 0.29:0.25

In 500 ml of distilled water 21.53 g Mn(NO₃)₂.6H20, 17.94 g Zn(NO₃)₂.6H₂O and 21.55 g ZrO(NO₃)₂.xH₂ O were dissolved. This solution was addedover the course of 30 minutes, with constant stirring, to 600 ml ofwater held at 70° C. The pH of this 600 mi was initially adjusted to pH9.0 with LiOH. Over the course of the addition, the addition rate of thetransition metal solution and of 1.0 Molar LiOH was controlled tomaintain a pH of 9.0. Stirring was continued for five hours at 70° C.The suspension was then allowed to settle and cool overnight. The palelight gray-brown precipitate was isolated by filtration. The filtratehad a pH of 8.72. The solids were resuspended in one liter of distilledwater and stirred vigorously for 30 minutes, then recovered byfiltration. The pH of the filtrate was 8.04. This washing step wasrepeated three times and the pH of the tiltrates were 7.58, 7.80 and8.45, respectively. The recovered solids were dried overnight at 130°C., leading to the recovery of 13.5 g of material. The dried materialwas ground to a fine powder and calcined in air in a tube furnace, thetemperature of which was raised from room temperature to 425° C. overthe course of two hours, held at 425° C. for two hours and allowed tocool to room temperature over the course of two hours. The material wastreated with 20 ml of distilled water in which 0.0814 g of Pd(NO₃)₂ wasdissolved along with 15 drops of ethanolamine. After thorough mixing,the slurry was dried in a vacuum oven for six hours. The dried materialwas then calcined in air as follows: the temperature was increased fromroom temperature to 325° C. over the course of an hour, then held at325° C. for three hours before cooling to room temperature over thecourse of two hours.

The BET surface area was 100 m² /g, and elemental analysis showed molefractions of the Mn, Zn, Zr and Li to be respectively 0.4634, 0.2891,0.2475 and >0.0001. The wt % Pd was 0.23%.

EXAMPLE 14 (Comparative) Preparation of Catalyst H with a Mn:Zn:Zr Ratioof 0.37: 0.38:0.25

In 500 ml of distilled water 43.06 g Mn(NO₃)₂.6H₂ O, 44.55 gZn(NO₃)₂.6H₂ O and 34.69 g ZrOCNO₃)₂.xH₂ O were dissolved, making asolution that was 0.90 Molar in transition metals. This solution addedover the course of 30 minutes, with constant stirring, to 600 ml ofwater held at 70° C. The pH of this 600 ml was initially adjusted to pH9.0 with LiOH. Over the course of the addition, the addition rate of thetransition metal solution and of 42.0 g LiOH.H₂ O/liter was controlledto maintain a pH of 9.0. Stirring was continued for five hours at 70° C.The suspension was allowed to cool and settle overnight. The precipitatewas isolated by filtration. The filtrate had a pH of 9.43. The solidswere resuspended in one liter of distilled water and stirred vigorouslyfor 30 minutes, then recovered by filtration. The pH of the filtrate was8.98. This washing step was repeated twice. The pH of the secondfiltrate was 8.61 and that of the final filtrate was 7.72. The solidswere dried overnight at 130° C. 35.63 g of dried, brownish black solidwere recovered. This material was ground to a fine powder. A portion ofthis material was calcined in air in a tube furnace, the temperature ofwhich was raised from room temperature to 425° C. over the course of twohours, held at 425° C. for two hours and allowed to cool to roomtemperature over the course of two hours. 20.16 g of cooled calcinedsolids were treated with 10 ml of distilled water in which 0.1263 g ofPd(NO₃)₂ was dissolved along with 20 drops of ethanolamine. Afterthrough mixing, the slurry was dried in a vacuum oven for six hours.After drying, the Pd-loaded solids were calcined in air, the temperatureof which was raised from room temperature to 425° C. over the course oftwo hours, held at 425° C. for two hours and allowed to cool to roomtemperature over the course of two hours. The resulting material had abulk atomic ratio of Mn to Zn to Zr to Li of 0.3675, 0.381, 0.2491 and0.001476 respectively.

EXAMPLE 15 (Comparative) Preparation of Catalyst I with an Mn:Zn:Zr:LiRatio of 0.25: 0.00: 0.65:0.10

In 500 ml of distilled water 41.0 g of 50% Mn(NO₃)₂.6H₂ O solution and58.0 g ZrO(NO₃)₂.xH₂ O were dissolved. This solution was added at therate of 200 drops/minute to 1000 mls of distilled water, the pH of whichhad previously been adjusted to 9.0 through the drop-wise addition of2.0 Molar LiOH solution. The pH of the mixture was maintained at 9.0through the continuous addition of 2.0 Molar LiOH solution. The mixturetemperature was maintained at about 70° C. throughout the addition. Theslurry containing the precipitate was aged overnight at 70° C. Thesolids were then recovered by filtration and the filtrate had a pH of6.98. The solids were resuspended in one liter of distilled water andstirred vigorously for 30 minutes before filtering. The filtrate had apH of 6.36. The washing step was repeated and the final filtrate had apH of 6.01. The gelatinous brownish maroon solid was dried overnight at130° C. 19.25 g of solids were recovered. These were finely ground andcalcined at 425° C. as in example above. 5 g of this solid were loadedwith Pd as above. The Pd-loaded and dried catalyst was heated in airwith the temperature increased from ambient to 325° C. over the course&one hour. The temperature was held at 325° C. for three hours, thencooled over the course of one hour.

This material had a surface area of about 206 m2/g, and the ratio ofmole fraction of Mn, Zr and Li respectively was 0.2467, 0.6487 and0.1041. The Pd loading was 0.23 wt %.

EXAMPLE 16 (Comparative) Preparation of Catalyst J with a Mn:Zn:Zr:LiRatio of 0.33: 0.00: 0.63:0.04

In 500ml of distilled water 41.1g Mn(NO₃)₂.6H20, and 115.6gZrO(NO₃)₂.xH₂ O were dissolved and added drop-wise to 500 ml of wateradjusted to pH 9.0 with LiOH. 42.0 g of LiOH.H₂ O dissolved in 1000 miof water was simultaneously added drop-wise (at about 1 drop per second)to the initial 500 ml so as to attempt to maintain a constant pH of 9.0.The temperature of the slurry was between about 60° C. and about 65° C.during the precipitation. The pinkish brown slurry was stirred overnightat 65° C. The recovered precipitate was washed three times with twoliters of distilled water and air dried for about 60 hours beforecalcining.

20g of the solid were loaded with Pd as follows: 0.1240g of Pd(NO₃)₂.2H₂O were dissolved in 20 ml of water along with 24 to 30 drops ofethanolamine. This was thoroughly mixed with 20.0 g of the calcinedmixed oxide and dried in a 130° C. vacuum oven for three hours prior tocalcination. The Pd-loaded and dried catalyst was heated in air with thetemperature increased from ambient to 325° C. over the course of onehour. The temperature was held at 325° C. for three hours, then cooledover the course of one hour.

This material had a surface area of about 92 m2/g, and the ratio of molefraction of Mn, Zr and Li respectively was 0.3293, 0.6288 and 0.0418.The Pd loading was 0.24 wt %.

EXAMPLE 17 (Comparative) Preparation of Catalyst K, ZnMn₂ O₄ Phase,Mn:Zn:Zr Ratio of0.68:0.32

In 500ml of distilled water 57.41gMn(NO₃)₂.6H₂ O and 29.70g Zn(NO₃)₂.6H₂O were dissolved, making a solution that was 0.6 Molar in transitionmetals with a pH of 2.32. This solution was added over the course of 30minutes, with constant stirring, to 600 ml of water held at 70° C. alongwith a 2.0 Molar LiOH solution. The pH of this 600 ml was initiallyadjusted to pH 9.0 with LiOH. Over the course of the addition, theaddition rate of the transition metal solution and of 2.0 Molar LiOH wascontrolled to maintain a pH of 9.0. Stirring was continued for fivehours at 70° C., then left unstirred to cool overnight. A creamy whitegel resulted. The precipitate was isolated by filtration. The filtratehad a pH of 7.27. On resuspension the solid darkened to orange brown.The filtrate from this washing had a pH of 7.79. After the secondwashing, the recovered air-dried orange brown powder was calcineddirectly, the temperature of which was raised from room temperature to425° C. over the course of two hours, held at 425° C. for two hours andallowed to cool to room temperature over the course of two hours. 13.79g of dry material were recovered. 14.81 g of this material were treatedwith 10 ml of distilled water in which 0.0927 g of Pd(NO₃)₂ wasdissolved along with 15 drops of ethanolamine. After thorough mixing,the slurry was dried in a vacuum oven for 1.25 hours, then calcined inair. Over the course of an hour, the temperature was increased from roomtemperature to 325° C., then held at 325° C. for three hours beforecooling to room temperature over the course of two hours.

The BET surface area was 35.7 m2/g, and elemental analysis showed molefractions of the Mn, Zn and Li to be respectively 0.6766, 0.3230 and0.0001. The wt % Pd was 0.21%.

EXAMPLE 18 (Comparative) Preparation of Protocatalyst L at pH 11 withMn:Zn:Zr Ratio of 0.42: 0.29:0.29

In 500 ml of distilled water 21.53 g Mn(NO₃)₂.6H20, I4.85 g Zn(NO₃)₂.6H₂O and 23.12 g ZrO(NO₃)₂.xH₂ O were dissolved. This solution was addedover the course of 30 minutes, with constant stirring, to 600 ml ofwater held at 70° C. The pH of this 600 ml was initially adjusted to pH11.0 with LiOH. Over the course of the addition, the addition rate ofthe transition metal solution and of a 21.0 g/500 ml solution of LiOH.H₂O (F.W. 41.96) was controlled to maintain a pH of 11.0. On addition ofthe transition metal solution and lithium hydroxide, the precipitateslurry was very light, almost white at the outset. The color slowlyturned brown as addition continued. The suspension was stirred for sixhours at 70° C. The suspension was allowed to settle for about 60 hoursat room temperature without stirring. The precipitate was isolated byfiltration, then washed three times by resuspension and stirring in aliter of distilled water for an hour at room temperature, followed byfiltering to recover the solids for further resuspension. The washedsolids were dried at 130° C. for about 64 hours. The driedbrownish-black material was ground to a fine powder and calcined in airin a tube furnace, the temperature of which was raised from roomtemperature to 425° C. over the course of two hours, held at 425° C. fortwo hours, and allowed to cool to room temperature over the course oftwo hours. 15.00 g of dry material were recovered. 15.0 g of thismaterial, ground to a fine powder, were treated with 15 ml of distilledwater in which 0.0930 g of Pd(NO₃)₂.xH₂ O (assay 39.95 wt % Pd) wasdissolved along with 15 to 20 drops of ethanolamine. It was thencalcined by heating over the course of one hour to 325° C., held at 325°C. for three hours, and then cooled to room temperature over the courseof one hour. After thorough mixing, the slurry was dried in a vacuumoven at 80° C. overnight.

Table 1 shows the composition and surface area of the catalysts.Composition is by relative atomic fraction of the metallic elements inthe mixed metal oxide phase(s) of the catalyst analyzed in theprotocatalyst. "MMF" means metal mold fraction. Preferred versions ofthe catalyst are designated A, B, and C.

                  TABLE 1                                                         ______________________________________                                        Catalyst Composition         Surface                                                                         Zr/   Zn/   Area                               Mn      Zn      Zr      Li     (Mn + (Mn + BET                                MMF     MMF     MMF     MMF    Zr)   Zr)   m.sup.2 /g                         ______________________________________                                        A   0.3841  0.2592  0.2954                                                                              0.061255                                                                             0.4347                                                                              0.3815                                                                              74.1                             B   0.3857  0.2706  0.3428                                                                              0.000963                                                                             0.4706                                                                              0.3714                                                                              75.1                             C   0.4202  0.2914  0.2884                                                                              --     0.4288                                                                              0.3838                                                                              72.1                             D   0.4023  0.2823  0.3154                                                                              --     0.4395                                                                              0.3933                                                                              78.8                             E   0.5390  0.2892  0.1674                                                                              0.004428                                                                             0.2370                                                                              0.4094                                                                              59.0                             F   0.2663  0.2184  0.5116                                                                              0.003681                                                                             0.6577                                                                              0.2808                                                                              112.2                            G   0.4634  0.2891  0.2475                                                                              --     0.3482                                                                              0.4067                                                                              100.0                            H   0.3675  0.3819  0.2491                                                                              0.001476                                                                             0.4040                                                                              0.6194                                                                              --                               I   0.2467  0.0000  0.6487                                                                              0.104117                                                                             0.7253                                                                              0.0000                                                                              206.2                            J   0.3293  0.0000  0.6288                                                                              0.041848                                                                             0.6563                                                                              0.0000                                                                              91.9                             K   0.6766  0.3230  0.0000                                                                              0.0001 0.0000                                                                              0.4773                                                                              35.7                             L   0.4165  0.2925  0.2910                                                                              --     0.5000                                                                              0.5000                                                                              67.9                             ______________________________________                                    

EXAMPLE 19

Table 2 is a comparison of the performance of catalysts within the scopeof the invention with catalysts with compositions outside the scope ofthe present invention. Reaction conditions were 3.00 cm³ of 60 to 80mesh catalyst volume in the copper-lined reactor tube, about 6500 kPa,44% CO, 39.4% H₂, 6.6% CO₂ and 10.0% Ar synthesis gas, into which wasvaporized at a rate of 0.8 liquid hourly space velocity a mixture of90.00 wt % methanol, 9.56 wt % ethanol and 0.44% water. Contact time isin seconds. Temperature is in ° C. iBuOH=isobutanol, MBuOH=methylbutanols, nPrOH=n-propanol, EtOH=ethanol. Others=other liquid products,including: n-butanol, n-pentanol, methyl pentanols, etc. CNV=ethanolconversion.

                                      TABLE 2                                     __________________________________________________________________________    Catalyst             C.sub.2 + Liquid Product                                 Mn:Zn:Zr  Reactor                                                                           Contact                                                                           CNV                                                                              Composition, Weight %                                    Atomic Fractions                                                                        Temp.                                                                             Time                                                                              %  iBuOH                                                                             MBuOH                                                                              nPrOH                                                                             EtOH                                                                             Others                                   __________________________________________________________________________    A         380 9.5 99.5                                                                             75  4    10  0.3                                                                              11                                       0.384:0.259:0.295                                                                       360 13.6                                                                              98.0                                                                             76  7    8   0.7                                                                              9                                        2M LiOH, 70° C. ppt                                                              340 13.3                                                                              94.6                                                                             75  8    5   4  8                                                  320 13.2                                                                              61.9                                                                             36  5    20  30 9                                        C         380 12.6                                                                              99.5                                                                             72  7    6   0.4                                                                              15                                       0.420:0.291:0.288                                                                       340 13.5                                                                              91.5                                                                             66  12   11  6  5                                        1M LiOH 70° C. ppt                                                     D         380 12.6                                                                              99.4                                                                             72  7    8   0.4                                                                              13                                       0.402:0.282:0.315                                                                       340 13.5                                                                              86.4                                                                             59  10   14  10 7                                        1M LiOH 25° C. ppt                                                     E         380 14.4                                                                              98.8                                                                             81  5    2   0.8                                                                              10                                       0.384:0.286:0.164                                                                       360 13.1                                                                              83.6                                                                             67  7    7   12 8                                        1M LiOH 70° C. ppt                                                               340 13.5                                                                              81.8                                                                             56  7    16  13 7                                        __________________________________________________________________________

EXAMPLE 20

Table 3 is a further comparison of preferred catalysts to otherPd-loaded Mn:Zn:Zr mixed oxide catalysts. Reaction conditions were 3.00cm³ of 60 to 80 mesh catalyst volume in the copper-lined reactor tube,about 6500 kPa, 44% CO, 39.4% H₂, 6.6 % CO₂ and 10.0% Ar synthesis gas,into which was vaporized at a rate of 0.8 liquid hourly space velocity amixture of 90.00 wt % methanol, 9.56 wt % ethanol and 0.44% water.Temperature is in ° C. iBuOH=isobutanol, MBuOH=methyl butanols,nPrOH=n-propanol, EtOH=ethanol. Others=other liquid products, including:n-butanol, n-pentanol, methyl pentanols etc. CNV=ethanol conversion.

                                      TABLE 3                                     __________________________________________________________________________                     C.sub.2 + Liquid Product                                                      Composition, Weight %                                        Catalyst   T °C.                                                                     CNV                                                                              iBuOH                                                                             MBuOH                                                                              nProH                                                                             EtOH                                                                             Others                                       __________________________________________________________________________    A          380                                                                              99.5                                                                             75  4    10  0.3                                                                              11                                           0.384:0.259:0.295                                                                        360                                                                              98.0                                                                             76  7    8   0.7                                                                              9                                            2M LiOH, 70° C. ppt                                                               340                                                                              94.6                                                                             75  8    5   4  8                                                       320                                                                              61.9                                                                             36  5    20  30 9                                            C          380                                                                              99.5                                                                             72  7    6   0.4                                                                              15                                           0.420:0.291:0.288                                                                        340                                                                              91.5                                                                             66  12   11  6  5                                            1M LiOH 25° C. ppt                                                     D          380                                                                              99.4                                                                             72  7    8   0.4                                                                              13                                           0.402:0.282:0.315                                                                        340                                                                              86.4                                                                             59  10   14  10 7                                            1M LiOH 70° C. ppt                                                     E          380                                                                              98.8                                                                             81  5    2   0.8                                                                              10                                           0.384:0.286:0.164                                                                        360                                                                              83.6                                                                             67  7    7   12 8                                            1M LiOH 70° C. ppt                                                     F          380                                                                              99.6                                                                             74  7    5   <1 13                                           0.266:0.218:0.512                                                                        340                                                                              77.7                                                                             48  8    16  17 11                                           G          380                                                                              99.5                                                                             70  7    7   <1 15                                           0.463:0.289:0.247                                                                        350                                                                              72.0                                                                             41  9    19  22 8                                            H          380                                                                              95.7                                                                             72  6    7   <1 14                                           0.367:0.382:0.249                                                                        340                                                                              82.6                                                                             48  9    16  16 11                                           __________________________________________________________________________

EXAMPLE 21

Table 4 is a comparison of Mn:Zn:Zr catalysts to catalysts lackingeither Zn or Zr. Reaction conditions were 3.00 cm³ of 60 to 80 meshcatalyst volume in the copper-lined reactor tube, about 6500 kPa, 44%CO, 39.4% H₂, 6.6% CO₂ and 10.0% Ar synthesis gas, into which isvaporized at a rate of 0.8 liquid hourly space velocity a mixture of90.00 wt % methanol, 9.56 wt % ethanol and 0.44% water. Contact time isin seconds. Temperature is in ° C. iBuOH=isobutanol, MBuOH=methylbutanols, nPrOH=n-propanol, EtOH=ethanol. Others=other liquid products,including: n-butanol, n-pentanol, methyl pentanols etc. CNV=ethanolconversion.

                                      TABLE 4                                     __________________________________________________________________________                     C.sub.2 + Liquid Product                                                      Composition, Weight %                                        Catalyst   T °C.                                                                     CNV                                                                              iBuOH                                                                             MBuOH                                                                              nProH                                                                             EtOH                                                                             Others                                       __________________________________________________________________________    A          380                                                                              99.5                                                                             75  4    10  0.3                                                                              11                                           0.384:0.259:0.295                                                                        360                                                                              98.0                                                                             76  7    8   0.7                                                                              9                                            2M LiOH, 70° C. ppt                                                               340                                                                              94.6                                                                             75  8    5   4  8                                                       320                                                                              61.9                                                                             36  5    20  30 9                                            I          380                                                                              99.5                                                                             72  5    9   0.3                                                                              13                                           0.247:0.000:0.649                                                                        360                                                                              94.5                                                                             73  6    6   4  1                                                       340                                                                              59.8                                                                             36  6    21  32 4                                            J 0.25% Pd 380                                                                              97.4                                                                             74  6    6   2  12                                           0.329:0.629                                                                              360                                                                              86.0                                                                             63  6    11  10 9                                                       340                                                                              56.6                                                                             36  5    17  35 6                                            K ZnMn.sub.2 O.sub.4                                                                     380                                                                              93.9                                                                             72  7    9   4  7                                            0.677:0.323:0.000                                                                        340                                                                              28.7                                                                             17  0    20  63 0                                            __________________________________________________________________________

EXAMPLE 22

Table 5 is a comparison of the preferred catalysts of this invention, Pdon Mn:Zn:Zr mixed oxide catalysts, to literature catalysts. Reactionconditions were 3.00 cm³ of 60 to 80 mesh catalyst volume in thecopper-lined reactor tube, about 6500 kPa, 44% CO, 39.4% H₂, 6.6% CO₂and 10.0% Ar synthesis gas, into which was vaporized at a rate of 0.8liquid hourly space velocity a mixture of 90.00 wt % methanol, 9.56 wt %ethanol and 0.44% water. Temperature is in ° C. iBuOH=isobutanol,MBuOH=methyl butanols, nPrOH=n-propanol, EtOH=ethanol. Others=otherliquid products, including: n-butanol, n-pentanol, methyl pentanols etc.CNV=ethanol conversion.

                                      TABLE 5                                     __________________________________________________________________________                        C.sub.2 + Liquid Product                                  Catalyst     Hrs on Composition, Weight %                                     MMF; Mn:Zn:Zr                                                                           T °C.                                                                     Line                                                                              CNV                                                                              iBuOH                                                                             MBuOH                                                                              nPrOH                                                                             EtOH                                                                             Others                                    __________________________________________________________________________    A         380                                                                               87 99.5                                                                             75  4    10  0.3                                                                              11                                        0.384:0.259:0.295                                                                       360                                                                              111 98.0                                                                             76  7    8   0.7                                                                              9                                         2M LiOH, 70° C. ppt                                                              340                                                                              120 94.6                                                                             75  8    5   4  8                                                   320                                                                              135 61.9                                                                             36  5    20  30 9                                         CeC.sub.2 Alfa                                                                          380                                                                              119 82.1                                                                             56  4    21  12 7                                                   360                                                                              143 32.6                                                                             16  3    19  59 3                                         MgO       380                                                                               2  88.1                                                                             70  2    18  8  1                                                   380                                                                               28 65.4                                                                             40  2    30  27 12                                        __________________________________________________________________________

EXAMPLE 23

Table 6 shows the impact of time under synthesis gas at about 380° C. onthe conversion of a protocatalyst into a catalyst. Reaction conditions:3.00 cm³ of 60 to 80 mesh catalyst volume in the copper-lined reactortube, about 6500 kPa, 44% CO, 39.4% H₂, 6.6% CO₂ and 10.0% Ar synthesisgas, into which is vaporized at a rate of 0.8 liquid hourly spacevelocity a mixture of 90.00 wt % methanol, 9.56 wt % ethanol and 0.44%water. Temperature is in ° C. Hours is hours at 380° C. under synthesisgas. iBuOH=isobutanol, MBuOH=methyl butanols, nPrOH=n-propanol,EtOH=ethanol. Others=other liquid products, including: n-butanol,n-pentanol, methyl pentanols, etc. CNV=ethanol conversion.

                                      TABLE 6                                     __________________________________________________________________________                        C.sub.2 + Liquid Product                                  Catalyst            Composition, Weight %                                     MMF; Mn:Zn:Zr                                                                           T °C.                                                                     Hrs CNV                                                                              iBuOH                                                                             MBuOH                                                                              nPrOH                                                                             EtOH                                                                             Others                                    __________________________________________________________________________    A         380                                                                               87 99.5                                                                             75  4    10  0.3                                                                              11                                        0.384:0.259:0.295                                                                       360                                                                              111 98.0                                                                             76  7    8   0.7                                                                              9                                         2M LiOH, 70° C. ppt                                                              340                                                                              120 94.6                                                                             75  8    5   4  8                                                   320                                                                              135 61.9                                                                             36  5    20  30 9                                         C         380                                                                               89 99.5                                                                             72  7    6   0.4                                                                              15                                        0.420:0.291:0.288                                                                       340                                                                              112 91.5                                                                             66  12   11  6  5                                         1M LiOH, 70° C. ppt                                                    C         340                                                                               18 85.4                                                                             57  9    13  11 10                                        0.420:0.291:0.288                                                             1M LiOH 70° C. ppt                                                     __________________________________________________________________________

EXAMPLE 24

Table 7 is a comparison of catalysts with preferred bulk compositionsprepared from oxide precursors precipitated under various conditions.Reaction conditions were 3.00 cem³ of 60 to 80 mesh catalyst volume inthe copper-fined reactor tube, about 6500 kPa, 44% CO, 39.4% H₂, 6.6%CO₂ and 10.0% Ar synthesis gas, into which is vaporized at a rate of 0.8liquid hourly space velocity a mixture of 90.00 wt % methanol, 9.56 wt %ethanol and 0.44% water. Temperature is in ° C. iBuOH=isobutanol,MBuOH=methyl butanols, nPrOH=n-propanol, EtOH=ethanol. Others=otherliquid products, including: n-butanol, n-pentanol, methyl pentanols,etc. CNV=ethanol conversion.

                                      TABLE 7                                     __________________________________________________________________________                      C.sub.2 + Liquid Product                                    Catalyst          Composition, Weight %                                       MMF; Mn:Zn:Zr                                                                             T °C.                                                                     CNV                                                                              iBuOH                                                                             MBuOH                                                                              nPrOH                                                                             EtOH                                                                             Others                                      __________________________________________________________________________    A           380                                                                              99.5                                                                             75  4    10  0.3                                                                              11                                          0.384:0.259:0.295                                                                         360                                                                              98.0                                                                             76  7    8   0.7                                                                              9                                           2M LiOH, 70° ppt                                                                   340                                                                              94.6                                                                             75  8    5   4  8                                                       320                                                                              61.9                                                                             36  5    20  30 9                                           C           380                                                                              99.4                                                                             72  7    8   0.4                                                                              13                                          0.420:0.294:0.288                                                                         340                                                                              86.4                                                                             59  10   14  10 7                                           1M LiOH 25° C. ppt                                                     D           380                                                                              99.5                                                                             72  7    6   0.4                                                                              15                                          0.402:0.282:0.315                                                                         340                                                                              91.5                                                                             66  12   11  6  5                                           1M LiOH 70° C. ppt                                                     L           380                                                                              99.4                                                                             73  7    7   0.4                                                                              12                                          0.417:0.292:0.291                                                                         340                                                                              75.1                                                                             44  8    19  19 10                                          pH 11.0 w LiOH 70° C. ppt                                              __________________________________________________________________________

What is claimed is:
 1. A catalyst composition, comprising: a noble metalsupported on at least a first phase having a poorly crystallinemanganese and zinc doped zirconium oxide phase containing about 71 toabout 91 atomic % zirconium, about 10 to about 16 atomic % manganese andabout 4 to about 8 atomic % zinc and a second phase of irregularlyshaped hetaerolite crystals containing about 65 to about 69 atomic %manganese, about 31 to about 35 atomic % zinc and 0 to about 5 atomic %zirconium embedded in the first phase.
 2. The composition of claim 1,wherein the zirconium oxide is selected from the group consisting ofcubic, tetragonal, and mixtures thereof.
 3. The composition of claim 1,wherein the first phase particles have a particle size of about 50 Å toabout 500 Å, and the second phase particles have a particle size of 500Å to 2000 Å.
 4. The composition of claim 1 wherein the mole ratio of Zrto the sum of the moles of Mn and Zr is between about 0.41 to about 0.50and the mole ratio of Zn to the sum of the moles of Mn and Zr is between0.29 and 0.40.
 5. The composition of claim 1 wherein the noble metal isselected from the group consisting of platinum and palladium.